JP2726769B2 - Air conditioning element and air conditioning container device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an air-conditioning element and an air-conditioning container apparatus which can control the concentration of gas such as humidity and oxygen arbitrarily and are used for various storage containers and various test containers. .

[0002]

2. Description of the Related Art In order to store clothes, metals and the like for a relatively long time without deteriorating the quality, it is necessary to prevent corrosion and mold of the storage container and to provide an optimum storage atmosphere in the storage container. It is necessary to keep The factors that determine the storage atmosphere are mainly humidity and oxygen concentration. Conventionally, the humidity of the storage atmosphere has been controlled by applying a desiccant described in, for example, US Pat. No. 4.307.425 or an electrolytic humidity adjusting element disclosed in JP-A-63-287527. However, there was no simple element or device for optimally controlling the ratio of humidity to oxygen concentration. Also, among various test container devices, there are devices that control temperature and humidity, but none control humidity and oxygen concentration optimally.

[0003]

In the conventional air conditioner and air conditioner described above, the humidity and temperature can be controlled but the oxygen concentration cannot be controlled. For example, water is electrolyzed and dehumidified in a container provided with an electric field type humidity control element, but the oxygen concentration increases as the humidity decreases. For this reason, the ratio of humidity and oxygen concentration in the container is not controlled, and there has been a problem that an optimum storage atmosphere cannot be maintained.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and there is provided a small air-conditioning element and a small air-conditioning container capable of controlling a ratio of humidity to oxygen concentration to maintain an optimum storage atmosphere. The purpose is to gain.

[0005]

The air conditioner according to the present invention comprises the following means. [1] A first electrode and a second electrode are joined to one surface of the cation conductive film, a third electrode and a fourth electrode are joined to the other surface, and a first electrode and a fourth electrode are joined to the first electrode. A first cell formed by bonding one constant activity layer. [2] A fifth electrode and a sixth electrode are joined to one surface of the anion conductive film, a seventh electrode and an eighth electrode are joined to the other surface, and a second electrode is joined to the fifth electrode. A constant activity layer is bonded to the first cell via an insulator.
Cell. The air-conditioning container device according to the present invention includes the following means. [3] A container in which the air conditioning element is joined to a partition. [4] A power supply and a control unit for detecting and controlling the gas concentration in the container through the air conditioning element.

[0006]

In the air conditioning element of the present invention, the first electrode and the second electrode are joined to one surface of the cation conductive film,
A first cell in which a third electrode and a fourth electrode are joined to the other surface and a first constant activity layer is joined to the first electrode is used to form the first constant activity layer and the first constant activity layer. The first battery is formed by the cationic conductive film and the gas adsorbed on the third electrode, and the gas is absorbed and released. Further, a fifth electrode and a sixth electrode are joined to one surface of the anion conductive film, a seventh electrode and an eighth electrode are joined to the other surface, and a second electrode is joined to the fifth electrode. The second cell joined to the first cell with the constant activity layer joined to the first cell with an insulator interposed between the second constant activity layer, the anion conductive film, and the seventh electrode. A second battery is formed with the adsorbed gas, and the gas is absorbed and released. Further, in the air-conditioning container device of the present invention, the gas concentration in the container is detected from the output of the first battery or the output of the second battery by the power supply and the control unit, and the second, fourth, and fourth gas are detected. A direct current is supplied to the sixth and eighth electrodes to control the gas concentration in the container.

[0007]

[Embodiment 1] Embodiment 1 of the present invention will be described with reference to the drawings. FIG. 1 is a sectional view showing the configuration of the first embodiment of the present invention. In FIG. 1, (1) is an air conditioning element, and (2A) and (2B) are air conditioning elements.
(1) is two cells, and (3) is an insulator joined between the cell (2A) and the cell (2B). (4) is cell (2A)
Is a hydrogen ion conductive film as a cation conductive film, for example, Nafion 117 (registered trademark of DuPont) manufactured by DuPont. (5a), (5b), (5c) and (5d)
Are second, third, first and fourth electrodes respectively bonded to the hydrogen ion conductive film (4), for example, a porous platinum plating film, and the electrodes (5a) and (5c ) Are bonded to one surface of the hydrogen ion conductive film (4) so that they do not contact each other, and the hydrogen ion conductive film (4) is bonded so that the electrodes (5b) and (5d) do not contact each other. It is joined to the other surface. (6) is a constant activity layer bonded to the electrode (5c), for example, potassium dihydrogen phosphate (KH ₂ PO ₄ ), which is a kind of hydrogen ion conductive solid, is used. (7a), (7
b), (7c) and (7d) are the electrodes (5a), (5b), (5c) and
This is the terminal joined to (5d). (8) is a hydroxide ion conductive film as an anion conductive film of the cell (2B), for example, a fluororesin film having an amino group. (9a),
(9b), (9c) and (9d) are hydroxide ion conductive membranes, respectively.
The sixth, seventh, fifth and eighth electrodes joined to (8), for example, a porous platinum plating film, so that the electrode (9a) and the electrode (9c) do not contact each other. One surface of the hydroxide ion conductive membrane (8) is joined, and the electrode (9b) and the electrode (9
d) so that the hydroxide ion conductive membrane does not contact with each other
It is joined to the other surface of (8). (10) is a constant activity layer bonded to the electrode (9c), for example, a mixture of calcium (Ca), which is a kind of hydroxide ion conductive solid, and calcium hydroxide in a predetermined ratio is used. ing. (11a), (11
b), (11c) and (11d) are terminals joined to the electrodes (9a), (9b), (9c) and (9d), respectively. (12) is a partition of a container, for example, a partition of a cassette of a magnetic disk device, a vegetable box of a refrigerator, etc. And the electrodes (5a), (5
The air conditioning element (1) is joined to a part of the partition (12) so that (c), (9a) and (9c) are on the side of the outside air (12B). (13) is a connector joined to a part of the bulkhead (12), (13a) to (13h)
Up to this is the terminal of the connector (13). (14) is a power supply and control unit, and (14a) to (14h) are terminals of the power supply and control unit (14). Terminal (7b) and terminal (13b), terminal (7d) and terminal (13
d), the terminal (11d) is connected to the terminal (13f), and the terminal (11b) is connected to the terminal (13h).

Next, the operation of the first embodiment will be described with reference to FIG. First, the principle of the air conditioning element (1) will be described. Electrode (5a) and electrode (9a) are cathode, electrode
The terminal (7a) and the terminal (11a) are connected to the terminal (14a) and the terminal (14g) of the power supply and control unit (14), respectively, so that the (5b) and the electrode (9b) become anodes, and the connector ( The terminal (13a) and the terminal (13g) of (13) are connected to the terminal (14b) and the terminal (14h) of the power supply and control unit (14), respectively. Power supply and control unit (14) to cell
When DC current is supplied to (2A) and the cell (2B), the electrode (5b)
And on the electrode (9b), reactions based on the equations (1) and (2) occur, respectively.

[0009]

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[0010]

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From the reaction based on the equation (1), at the electrode (5b), water (H ₂ O) in the space (12A) in the container is decomposed into oxygen (O ₂ ) and hydrogen ions (H ⁺ ). The obtained oxygen is stored in the container space (12
The hydrogen ions remaining in A) move through the hydrogen ion conductive film (4), react with oxygen in the outside air (12B) on the electrode (5a), and are released into the outside air (12B). Further, from the reaction based on the formula (2), water and oxygen are generated from the hydroxide ion (OH ⁻ ) of the hydroxide ion conductive membrane (8) at the electrode (9b), and the water and oxygen are introduced into the space (12A) in the container. Released.

Here, assuming that a current between the electrode (5a) and the electrode (5b) is x and a current between the electrode (9a) and the electrode (9b) is y, the electrode (5
b) each amount delta ₂ of water and oxygen obtained by reaction in the amount of water and oxygen to react delta ₁ and the electrodes (9b) in
It is represented by equations (3) and (4).

[0013]

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[0014]

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That is, dehumidification and release of oxygen occur at the electrode (5b) in proportion to the current x, and humidification and release of oxygen occur at the electrode (9b) in proportion to the current y. Therefore, the variation delta ₃ of water and oxygen in the container space (12A) is represented by equation (5).

[0016]

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Further, the ratio K of the amount of change between water and oxygen is expressed by equation (6).

[0018]

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From equation (6), the ratio K of the amount of change between water and oxygen is:
It changes depending on the values of the currents x and y. That is, the ratio K of the amount of change between water and oxygen is arbitrarily changed by controlling the direct current supplied from the power supply and the control unit (14) to the cells (2A) and (2B). Therefore, the ratio between the humidity and the oxygen concentration in the container interior space (12A) can be changed by controlling the direct current supplied to the cells (2A) and (2B).

Next, the detection of the humidity and the oxygen concentration in the space (12A) in the container will be described. When the cell (2A) is used, the terminal (7c) of the electrode (5c) is connected to the terminal (1) of the power supply and control unit (14).
4c), and connect the terminal (13c) of the connector (13) to the terminal (14d) of the power supply and control unit (14). First, detection of humidity will be described. Power supply and control unit (14), terminal (14a)
It is set so that the specific resistance can be measured from (14b).
Nafion 11 used for hydrogen ion conductive membrane (4)
7 also plays a role as a humidity sensor because the specific resistance changes according to the humidity. Utilizing this, the power supply and control unit (14) detects the humidity of the space (12A) in the container from the measured specific resistance of the hydrogen ion conductive film (4).

Next, detection of the oxygen concentration will be described.
The power supply and control unit (14) is set so that the voltage between the terminals (14a) and (14b) can be measured. The electrode (5d) has a space inside the container (1
The amount of oxygen corresponding to the oxygen concentration of 2A) is adsorbed, and the following battery is formed by the hydrogen ion conductive film (4), the constant activity layer (6) and the adsorbed oxygen. Constant activity layer | Hydrogen ion conductive membrane | Because KH ₂ PO ₄ used in the adsorbed oxygen constant activity layer has a constant hydrogen ion activity, it is adsorbed between the terminal (7c) and the terminal (7d). A voltage corresponding to the amount of oxygen is generated. Specifically, the adsorbed oxygen is a function of the space (12A) in the container, and the voltage between the terminal (7c) and the terminal (7d) indicates a value proportional to the logarithm of the oxygen concentration. Utilizing this, the power supply and control unit (14)
From the voltage measured between (14a) and terminal (14b),
The oxygen concentration of 2A) is detected.

On the other hand, when the cell (2B) is used, the electrode
Connect the terminal (11c) of (9c) to the terminal (14e) of the power supply and control unit (14), and connect the terminal (13e) of the connector (13) to the power supply and control unit.
Connect to terminal (14f) of (14). Hydroxide ion conductive membrane
With regard to (8), the humidity of the container interior space (12A) can be detected in the same manner as the hydrogen ion conductive membrane (4). Also,
The oxygen concentration depends on the Ca (OH) ₂ used in the constant activity layer (10).
Is a constant hydroxide ion activity, the constant activity layer (1
0), the hydroxide ion conductive membrane (8) and oxygen adsorbed on the electrode (9d) are detected by measuring the voltage of the battery.

The oxygen concentration in the container space (12A) can be detected by either one of the cells (2A) and (2B). You may select and go. As described above, the first embodiment
Then, while detecting the oxygen concentration, the cell (2
By controlling the direct current to A) and (2B), the ratio K of the humidity and the oxygen concentration of the space (12A) in the container can be controlled.

Embodiment 2 FIG. Note that when the container space (12A) is relatively high (200 ° C. or higher), a hydrogen ion conductive film (4) as a ceramic membrane, for example a _{SrCe 0. 95 Yb 0. 05} O 3-2 using A ceramic film as the hydroxide ion conductive film (8), for example, (Bi ₂ O ₈ )
_{Using 1-x} (Y ₂ O ₃ ) _x , a mixture of a metal and a metal oxide, for example, nickel (Ni) and nickel oxide (Ni
When a mixture with O) is used, the same effect as in the first embodiment can be obtained.

Embodiment 3 FIG. Further, when at least one of the electrodes (5a) to (5d) and the electrodes (9a) to (9d), a mixed conductor of ions and electrons, for example, a chalcogen compound of silver (Ag) is used. Hydrogen ion conductive film (4) or hydroxide ion conductive film
(8) Only ions move in the inside and the movement of molecules is suppressed, so that the current efficiency is improved and the constant activity layer is further stabilized, so that the humidity and oxygen concentration can be accurately controlled. .

Embodiment 4 FIG. Further, in the first embodiment, KH ₂ PO ₄ is used for the constant activity layer (6), but the same effect can be obtained by absorbing a predetermined amount of hydrogen and using a hydrogen storage alloy.

Embodiment 5 FIG. In Example 1, when an oxygen ion conductive film is used instead of the hydroxide ion conductive film (8), only the oxygen concentration can be controlled.

Further, in Example 1, the humidity and oxygen concentration are controlled by using Nafion 117 for the cationic conductive film of the present invention and using a fluorine-based resin having an amino group for the anionic conductive film. Other cation conductive solids or cation exchange membranes or other anion conductive solids or anion exchange membranes can be used to control gas concentrations other than humidity and oxygen concentration. For example, when a fluorine ion conductive film (such as LdF ₃ ) is used as the anion conductive film, the space inside the container (12A)
Can be controlled.

Embodiment 6 FIG. If a plurality of air-conditioning elements that absorb and release various gases are joined to the partition (12), the concentration of multi-component gas can be controlled.

[0030]

As described above, the air-conditioning element of the present invention has the first electrode and the second electrode on one surface of the cation conductive film.
A first cell in which a third electrode and a fourth electrode are joined to the other surface, and a first constant-activity layer is joined to the first electrode; The fifth electrode and the sixth electrode are joined to one surface of the conductive film, the seventh electrode and the eighth electrode are joined to the other surface, and the second electrode is joined to the fifth electrode.
And a second cell joined to the first cell via an insulator.
There is an effect that a small product can be obtained.

Further, the air-conditioning container device of the present invention includes a container in which the air-conditioning element is joined to a partition, and a power supply and a control unit for controlling the gas concentration in the container through the air-conditioning element. The effect of controlling the ratio of the humidity and the oxygen concentration in the space to maintain an optimal storage atmosphere can be achieved.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a configuration of a first exemplary embodiment of the present invention.

[Explanation of symbols]

 (1) Air conditioning element (2A), (2B) Cell (3) Insulator (4) Hydrogen ion conductive membrane (5a)-(5d) Electrode (6), (10) Constant activity layer (8) Hydroxidation Ion conductive membrane (9a)-(9d) Electrode (12) Container partition (12A) Container space (14) Power supply and control unit

Claims (2)

(57) [Claims] 1. A first electrode and a second electrode are joined to one surface of a cationic conductive film, and a third electrode and a fourth electrode are joined to the other surface. A first cell in which a first constant activity layer is bonded to the first electrode, a fifth electrode and a sixth electrode bonded to one surface of the anion conductive film, and a seventh electrode to the other surface. And the eighth electrode are joined,
An air conditioner comprising: a second cell formed by joining a second constant activity layer to a fifth electrode and joining the first cell via an insulator. 2. An air conditioner, comprising: a container in which the air conditioning element according to claim 1 is joined to a partition; and a power supply and a control unit for detecting and controlling a gas concentration in the container through the air conditioning element. Container device.